JP2009242675A - Adhesive for moisture permeable water proofing cloth - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive which has a reduced load on a working environment and atmosphere, and can obtain a moisture permeable water proofing cloth having moisture permeability, water proofing properties and washing resistance equal to or above those of the conventional organic solvent solution type polyurethane resin adhesive. <P>SOLUTION: The adhesive for a moisture permeable water proofing cloth includes: an alcohol solution composed of a hydrophilic polyurethane resin (A) formed from a polymer diol (a) including an oxyethylene group-containing polymer diol (a1), aliphatic and/or alicyclic diisocyanate (b) and a chain extender (c) consisting of aliphatic and/or alicyclic diamine, and an alcohol solvent (B); and polyisocyanate (C). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an adhesive for moisture-permeable waterproof fabrics.

  Conventionally, a non-porous moisture-permeable waterproof fabric made of a moisture-permeable polyurethane resin is coated with a moisture-permeable polyurethane resin solution on a fiber fabric and then dried, or a release paper is coated with a moisture-permeable polyurethane resin solution. It was produced by post-drying and adhering the polyurethane resin film obtained as a skin material (moisture permeable waterproof layer) to a fiber fabric with an organic solvent solution type polyurethane resin adhesive (for example, Patent Documents 1 and 2). reference). Generally, as the organic solvent for the adhesive, dimethylformamide (DMF), toluene (TOL), methyl ethyl ketone (MEK), etc. are used. When producing a moisture-permeable waterproof fabric, the organic solvent is used in exhaust and waste water. As a result, the work environment is deteriorated and air pollution is occurring. Then, the water-based adhesive composition (for example, refer patent document 3) is proposed as what does not use an organic solvent.

Japanese Unexamined Patent Publication No. 64-62320 Japanese Patent Laid-Open No. 3-203920 JP 2007-77191 A

  However, in the method of coating the fiber cloth with the moisture-permeable polyurethane resin solution and then drying, it is difficult to control the penetration of the resin solution into the fiber cloth. Therefore, the moisture-permeable waterproof cloth obtained has sufficient moisture permeability. However, there is a drawback that the texture becomes hard. Further, in the method using the water-based adhesive composition, the moisture permeability, waterproofness and washing resistance of the moisture permeable waterproof fabric obtained compared with the case of the conventional organic solvent solution type polyurethane resin are not sufficient, so that it is still practical. The current situation is that it has not yet been realized.

  An object of the present invention is to obtain a moisture-permeable waterproof fabric that has a small load on the work environment and the atmosphere and has moisture permeability, waterproofness and washing resistance equal to or higher than that of a conventional organic solvent solution type polyurethane resin adhesive. It is to provide an adhesive that can be used.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention provides the following 1. ~ 4. About.

  1. A chain extender comprising a polymer diol (a) containing a polymer diol (a1) having an oxyethylene group, an aliphatic and / or alicyclic diisocyanate (b), and an aliphatic and / or alicyclic diamine ( A moisture-permeable waterproof fabric adhesive comprising a hydrophilic polyurethane resin (A) formed from c) and an alcohol solution consisting of an alcohol solvent (B) and a polyisocyanate (C).

  2. Through the adhesive layer formed of the adhesive described in 1 above, at least a part of at least one side of the fiber fabric and a moisture permeable waterproof layer made of polyurethane resin are bonded, or moisture permeable waterproof made of polyurethane resin. A moisture-permeable waterproof fabric in which at least a part of both surfaces of a layer is bonded to a plurality of fiber fabrics.

  3. At least one surface of one side of the fiber fabric is formed on the surface of the laminate formed by laminating the release paper, the moisture-permeable waterproof layer made of polyurethane resin, and the adhesive layer formed of the adhesive described in 1 above in this order. A method for producing a moisture-permeable waterproof fabric, wherein the release paper is peeled off after the portions are bonded together.

The moisture-permeable waterproof fabric adhesive of the present invention has the following effects.
(1) Since the solvent used is alcohol, the load on the work environment and the atmosphere is small.
(2) Excellent adhesion between the moisture permeable waterproof layer and the fiber fabric.
(3) The moisture-permeable waterproof fabric using the adhesive is excellent in moisture permeability, waterproofness and washing resistance, and has a soft texture.

  Hereinafter, preferred embodiments of the present invention will be described, but it should be understood that the present invention is not limited to these embodiments, and that various modifications can be made within the spirit and scope of the present invention. .

Alcohol solution of hydrophilic polyurethane resin (A) The alcohol solution comprising the hydrophilic polyurethane resin (A) soluble in alcohol and the alcohol solvent (B) in the present invention contains a polymer diol (a1) having an oxyethylene group. A hydrophilic polyurethane resin (a) formed from a polymer diol (a), an aliphatic and / or alicyclic diisocyanate (b), and a chain extender (c) comprising an aliphatic and / or alicyclic diamine ( A polyurethane resin solution comprising A) and an alcohol solvent (B). In the present invention, “soluble in alcohol” means that 10 g or more of polyurethane resin is dissolved in 100 g of alcohol.

  The oxyethylene group (hereinafter abbreviated as OE group) content in the polymer diol (a1) is preferably at least 30%, more preferably based on the weight of the polymer diol (a) from the viewpoint of moisture permeability. At least 40%.

  Examples of the polymer diol (a1) include polyoxyethylene glycol (hereinafter abbreviated as PEG), polyoxyethyleneoxypropylene block copolymerized diol (hereinafter abbreviated as PEPG), polyoxyethyleneoxytetramethylene block copolymerized diol, and ethylene oxide. (Hereinafter abbreviated as EO) and propylene oxide (hereinafter abbreviated as PO), random copolymer diol of EO and tetrahydrofuran (hereinafter abbreviated as THF); ethylene glycol, propylene glycol, 1,4-butanediol 1,6-hexamethylene glycol (hereinafter abbreviated as EG, PG, 1,4-BD, 1,6-HD), bis (hydroxymethyl) cyclohexane, 4,4'-bis (2-hydroxyethoxy)- Diphenylpropane etc. EO adduct of low-molecular glycol; number average molecular weight [hereinafter abbreviated as Mn (OH value); hereinafter, values other than polyurethane resin are determined from hydroxyl value (OH value)] 1,000 or less PEG and dicarboxylic acid [ Condensed polyetherester diol obtained by reacting carbon number (hereinafter abbreviated as C) 2 to 12, for example, succinic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid]; and a mixture of two or more thereof Is mentioned. Among these, from the viewpoint of moisture permeability, PEG, PEPG, and polyoxyethyleneoxytetramethylene block copolymer diol are preferable, and PEG and PEPG are particularly preferable.

  The Mn (OH value) of (a1) is preferably 500 to 20,000, more preferably 700 to 15,000, from the viewpoint of the strength and moisture permeability of the adhesive layer coating film.

  The polymer diol (a) includes a polymer diol (a2) other than (a1) as long as moisture permeability is not inhibited.

  Examples of (a2) include polyether diols (a21) other than (a1), polyester diols (a22), polycarbonate diols (a23), and mixtures thereof.

  Of the polymer diol (a2), examples of the polyether diol (a21) include polyoxypropylene glycol, polyoxytetramethylene glycol (hereinafter abbreviated as PTMG), polyoxypropyleneoxytetramethylene block copolymer diol, and the like. The mixture of 2 or more types of these is mentioned.

  Examples of the polyester diol (a22) include polyethylene adipate, polybutylene adipate, poly 2,2-dimethyltrimethylene adipate, poly-3-methylpentamethylene adipate, polyhexamethylene adipate, polycaprolactone diol, and two or more thereof. Of the mixture.

Examples of the polycarbonate diol (a23) include polyhexamethylene carbonate diol.
The preferable Mn (OH value) of the polymer diol (a2) is the same as the Mn (OH value) of the polymer diol (a1).

  The proportion based on the weight of the polymer diol (a) is usually 15% or more, preferably 30 to 100%, more preferably 40 to 100% from the viewpoint of moisture permeability and waterproofness, and (a2) is usually 85% or less, preferably from 0 to 70%, more preferably from 0 to 60% from the viewpoint of waterproofness and moisture permeability.

  In the present invention, aliphatic and / or alicyclic diisocyanate (hereinafter sometimes abbreviated as DI) (b) includes C (excluding carbon in the NCO group, the same shall apply hereinafter) 6-12 aliphatic DI (b1 ), C6-15 alicyclic DI (b2) and mixtures of two or more thereof.

  Examples of (b1) include hexamethylene DI (HDI), dodecamethylene DI, 2,2,4-trimethylhexamethylene DI, lysine DI, 1,3,6-trimethylhexamethylene DI, and the like.

  (B2) includes isophorone DI (hereinafter abbreviated as IPDI), dicyclohexylmethane-4,4′- and / or 2,4′-DI, 1,4-cyclohexane DI, methylcyclohexane-2,4-DI, 1 , 4-bis (2-isocyanatoethyl) cyclohexane and the like.

  Of these, alicyclic diisocyanates are preferable from the viewpoint of water resistance and heat resistance, and IPDI is more preferable.

  Examples of the chain extender (c) composed of aliphatic and / or alicyclic diamine include aliphatic diamine (C2-12, for example, ethylenediamine, trimethylhexamethylenediamine), alicyclic diamine [C5-15, for example, 1 , 4-diaminocyclohexane, isophoronediamine (hereinafter abbreviated as IPDA), 4,4′- and / or 2,4′-diaminodicyclohexylmethane (hereinafter abbreviated as DADCHM)], hydrazine, and two or more thereof A mixture is included. Of these, from the viewpoints of water resistance and heat resistance, preferred are alicyclic diamines, and more preferred are IPDA and DADCHM.

  Examples of the alcohol solvent (B) include primary alcohols (C1-10, such as methanol, ethanol, n-propyl alcohol, n-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), and secondary alcohols. Alcohol [C3-10, for example, isopropyl alcohol (hereinafter abbreviated as IPA), sec-butyl alcohol, propylene glycol monomethyl ether (hereinafter abbreviated as MPG), propylene glycol monoethyl ether (hereinafter abbreviated as EPG), propylene glycol monopropyl ether (Hereinafter abbreviated as PPG)], tertiary alcohol [C4-10, for example, t-butyl alcohol (hereinafter abbreviated as t-BA)], and a mixture of two or more thereof.

  Among these, from the viewpoint of non-reactivity with the NCO group in (b), preferred are secondary and tertiary alcohols, and mixtures of two or more thereof, more preferred are IPA, MPG, EPG, PPG, t-BA and a mixture of two or more thereof.

  The oxyethylene group content of the hydrophilic polyurethane resin (A) is preferably 5% or more, more preferably 10% or more, particularly preferably 15% or more based on the weight of (A), from the viewpoint of moisture permeability. From the viewpoint of the strength of the layer coating film, it is preferably 50% or less, more preferably 45% or less, and particularly preferably 40% or less.

Here, the oxyethylene group content of (A) is calculated according to the following formula.
(A) Oxyethylene group content (% by weight) =
[Weight of (a1)] × [OE group content (% by weight) of (a1)] / [Weight of (A)]

In the formation of the hydrophilic polyurethane resin (A), the reaction equivalent ratio of the diisocyanate (b) and the polymer diol (a) is the heat resistance of (A) and the suppression of penetration into the fiber fabric during adhesive coating. From the viewpoint, it is preferably 1.1 / 1 to 2/1, more preferably 1.2 / 1 to 1.8 / 1, and the reaction equivalent ratio of (b) to [(a) + (c)] Is preferably 0.9 / 1 to 1.1 / 1, more preferably 0.95 / 1 to 1.07 / 1, from the viewpoint of the molecular weight and mechanical properties of (A).
(A) is obtained by reacting (b), (a), and (c) at the above equivalent ratio by the production method described later. The molecular end of (A) after the reaction is preferably an OH group from the viewpoint of reactivity with polyisocyanate (C). When NCO groups are present at both ends or at one end when (A) reaches the target molecular weight, an OH group is formed at the molecular end by reacting an alkanolamine or low molecular glycol described later with an NCO group. Is introduced.

  The number average molecular weight of the hydrophilic polyurethane resin (A) [hereinafter abbreviated as Mn, measured by gel permeation chromatography (GPC) method] is from the viewpoint of the strength of the adhesive layer coating film and the viscosity of the polyurethane resin solution described later. , Preferably 5,000 to 300,000, more preferably 7,000 to 250,000.

Although the measurement by said GPC method is not specifically limited, For example, it measures on the following conditions.
Measuring instrument: HLC-8220 [manufactured by Tosoh Corporation]
Column: Trade name “TSKgel α-M”, manufactured by Tosoh Corporation Solvent: Dimethylformamide (DMF)
Standard material: polystyrene Column temperature: 40 ° C

  As a manufacturing method of hydrophilic polyurethane resin (A), a normal method, for example, aliphatic and / or alicyclic diisocyanate (b), polymeric diol (a), and chain extender (c) are made to react simultaneously. Examples thereof include a one-shot method and a prepolymer method in which (b) and (a) are reacted first and then (c) is continuously reacted. Among these, the prepolymer method is preferable from the viewpoint of Mn of the hydrophilic polyurethane resin (A). The above reaction can be carried out in the presence or absence of a solvent. As the solvent in the presence of the solvent, the alcohol solvent (B) which is added to form the alcohol solution (A) in the subsequent step is preferable.

  Said (A) is manufactured using the normal manufacturing apparatus in which the said urethanation reaction is possible, and when not using a solvent, manufacturing apparatuses, such as a kneader and an extruder, can be used.

  In the production of the hydrophilic polyurethane resin (A), the reaction temperature may be the same as in a normal urethanization reaction, usually 20 to 100 ° C. when using a solvent, and usually 20 to 220 ° C. when no solvent is used. is there.

  In order to promote the reaction, various urethanization reaction catalysts such as amine catalysts (triethylamine, triethylenediamine, etc.), tin catalysts (dibutyltin dilaurate, etc.) can be used as necessary.

Moreover, low molecular glycol or alkanolamine can be used as a reaction terminator in order to complete the reaction as required and introduce an OH group at the molecular end.
Examples of the low molecular glycol include C2-10, such as EG, PG, and 1,4-BD. Examples of the alkanolamine include C2-10, such as monoethanolamine and diethanolamine. Of these, alkanolamine is preferable from the viewpoint of reactivity.

  The hydroxyl value of (A) (unit is mgKOH / g, in the following, only numerical values are described) is preferably 0.5 to 25, more preferably 1 to 18, from the viewpoint of coating strength and coating texture. Especially preferably, it is 1.5-15.

The alcohol solution (A) or (A) is usually prepared as an alcohol solution of the hydrophilic polyurethane resin (A) having a predetermined resin concentration by further adding an alcohol solvent (B).
The concentration (% by weight) is preferably 10 to 70, more preferably 20 to 65, from the viewpoint of suppressing penetration into the fiber fabric during adhesive coating and handling properties during adhesive coating. The solution viscosity (Pa · s / 20 ° C.) is preferably 1 to 500, more preferably 3 to 300, from the same viewpoint as described above.

Polyisocyanate (C)
Examples of the polyisocyanate (C) in the present invention include the above-mentioned diisocyanate (b), a urethane-modified product obtained by reacting the diisocyanate (b) and trimethylolpropane (TMP) at a molar ratio of 3/1 [for example, HDI or IPDI. A modified product obtained by reacting TMP with TMP, specifically, “Duranate WB40-100” (HDI urethane modified product, hereinafter abbreviated as WB40-100), “Duranate P-301-75E” [Asahi Kasei Kogyo Co., Ltd.] Manufactured by Co., Ltd.], trade name “Coronate HL” [Nippon Polyurethane (manufactured)] etc.], (b) and a burette modified product obtained by reacting water at a molar ratio of 3/1 [for example, HDI or IPDI and water. Reacted modified products, such as the product name “Sumijour N-100” (manufactured by Sumitomo Bayer Urethane Co., Ltd.), the product name “DU Nate 24A-100 ”[manufactured by Asahi Kasei Kogyo Co., Ltd.], etc.], isocyanurate modified product of (b) [for example, HDI or IPDI trimer, specifically trade name“ Sumijour N-3500 ”[Sumitomo Bayer Urethane Co., Ltd.], trade name “Duranate TPA-100” [Asahi Kasei Kogyo Co., Ltd.], etc.], modified products obtained by reacting these modified products with hydrophilic monools or diols (for example, the urethane described above) Denatured product obtained by reacting a modified product, a burette modified product or an isocyanurate modified product with a hydrophilic monool [5-100 mol adduct of alcohol (methanol, ethanol, etc.)] at a molar ratio of 1 / (0.5-1). A modified body obtained by reacting the urethane-modified body, the burette-modified body or the isocyanurate-modified body with a hydrophilic diol such as PEG at a molar ratio of 2/1] Dimers of the above-mentioned modified products [for example, modified products obtained by reacting the urethane-modified product, burette-modified product or isocyanurate-modified product with EG, 1,4-BD at a molar ratio of 2/1, etc.] Body trimers [for example, urethane-modified HDI, burette-modified, or isocyanurate-modified and TMP reacted with TMP at a molar ratio of 3/1], and mixtures of two or more thereof It is done.

  Among these, from the viewpoints of the stability of the adhesive of the present invention and the chemical resistance and heat resistance of the resulting adhesive layer coating film, preferred are HDI urethane-modified, burette-modified, isocyanurate-modified, IPDI, isocyanurate-modified products, modified products obtained by reacting these modified products with hydrophilic monools or diols, and mixtures of two or more thereof.

  The polyisocyanate (C) is used in an equivalent ratio of [NCO group of (C) and OH group of (A) [NCO / OH equivalent ratio] from the viewpoint of peel strength, washing resistance and texture of moisture-permeable waterproof fabric. Is preferably 0.5 / 1 to 20/1, more preferably 1/1 to 18/1.

Additive (D)
The adhesive for moisture-permeable waterproof fabrics of the present invention can contain an additive (D) that is usually used for an adhesive, if necessary, as long as the effects of the present invention are not impaired.
Examples of (D) include a weather stabilizer (D1) (an antioxidant, an ultraviolet absorber, a light stabilizer, etc.) and a heat resistant stabilizer (D2).
(D) The total amount used is usually 6% or less, preferably 0.05 to 4%, based on the total weight of the adhesive of the present invention.

(D1) includes hindered phenolic antioxidants [trade name “Sumilyzer BHT”, manufactured by Sumitomo Chemical Co., Ltd.]; trade names “Yoshinox BB”, manufactured by Yoshitomi Pharmaceutical Co., Ltd.], benzotriazole UV absorption Agent [trade name “Tinuvin P”, manufactured by Ciba Specialty Chemicals Co., Ltd .; trade name “Sumisorb 320”, manufactured by Sumitomo Chemical Co., Ltd.], hindered amine light stabilizer [trade name “Tinuvin 765”, trade name “Tinubin 144”, all manufactured by Ciba Specialty Chemicals Co., Ltd.] and the like.
The amount of (D1) used is usually 3% or less, preferably 0.05-2%, based on the total weight of the adhesive of the present invention.

Examples of (D2) include phosphorus compound heat stabilizers [trade name “Irgafos 168”, trade name “Irgafos 38”, all manufactured by Ciba Specialty Chemicals Co., Ltd.], etc.], lactone compound heat stabilizers [trade name “Irgastab” PUR68 ", trade name" Irganox HP2215 ", all manufactured by Ciba Specialty Chemicals Co., Ltd.] and the like.
The amount of (D2) used is usually 3% or less, preferably 0.05-2%, based on the total weight of the adhesive of the present invention.

Method for Producing Adhesive The adhesive of the present invention can be produced by batch-mixing and mixing an alcohol solution of the hydrophilic polyurethane resin (A), polyisocyanate (C) and, if necessary, additive (D). . In this case, the mixing may be mixing by ordinary stirring alone, or may be mixing using a mixing device (ball mill, kneader, sand blaster, roll mill, etc.).

Moisture permeable waterproof fabric The form of the moisture permeable waterproof fabric of the present invention includes a moisture permeable waterproof fabric comprising at least a part of at least one side of a fiber fabric and a polyurethane resin via an adhesive layer formed from the adhesive for moisture permeable waterproof fabric. Examples include those in which a waterproof layer is bonded, or in which at least a part of both surfaces of a moisture permeable waterproof layer made of polyurethane resin is bonded to a plurality of fiber fabrics.
Here, the thickness of the adhesive layer is preferably 5 to 50 μm, more preferably 10 to 40 μm, from the viewpoint of water resistance and texture.

  Examples of the fiber fabric include fabrics made of natural fibers or synthetic fibers. Specific examples include fabrics made of fibers such as cotton, suf, polyester, nylon, and acrylic, and blended, blended, and interwoven fabrics made of two or more of these fibers. Examples of fiber fabrics include woven fabrics, knitted fabrics, nonwoven fabrics, and raised fabrics, and these fiber fabrics may be in a laminated form having a porous film of polyurethane resin or polytetrafluoroethylene on at least one surface thereof. In addition, these fiber fabrics may be subjected to a water repellent treatment with silicon resin, fluorine resin or the like in order to prevent excessive penetration of the adhesive into the fiber fabric.

  The moisture permeable waterproof layer made of the polyurethane resin includes various known ones, preferably those using alcohol as a solvent (Japanese Patent Laid-Open No. 2007-2111239, etc.), water-based polyurethane resins, and none. A moisture-permeable waterproof layer using polyurethane resin obtained by heat-forming with a solvent (suppressing release of DMF, MEK, TOL, etc. into the exhaust and waste water during manufacture of the moisture-permeable waterproof layer) can be used. .

As a manufacturing method of the moisture-permeable waterproof fabric of this invention, the following method is mentioned corresponding to the form of the said moisture-permeable waterproof fabric.
(1) Method for producing moisture-permeable waterproof fabric in which at least part of one side of fiber fabric and moisture-permeable waterproof layer made of polyurethane resin are bonded Release paper, moisture-permeable waterproof layer made of polyurethane resin, and adhesion of the present invention Moisture permeable waterproofing characterized in that at least a part of one side of the fiber fabric is bonded to the adhesive layer side surface of the laminate formed by laminating the adhesive layers formed from the agent in this order, and then the release paper is peeled off A method for producing a fabric, specifically, a step of applying a polyurethane resin-forming composition onto a release paper to form a moisture permeable waterproof layer, and applying the adhesive of the present invention on the moisture permeable waterproof layer Forming a bonding layer, a step of attaching at least a part of one side of the fiber fabric to the bonding layer, and a step of peeling the release paper.

(2) Method for producing a moisture permeable waterproof fabric in which at least a part of both surfaces of a fiber fabric and a plurality of moisture permeable waterproof layers made of polyurethane resin are bonded to each other. A polyurethane resin-forming composition is coated on a release paper. A step of forming a moisture permeable waterproof layer, a step of applying the adhesive of the present invention on the moisture permeable waterproof layer to form an adhesive layer, and the moisture permeable waterproof fabric obtained in (1) above on the adhesive layer. A manufacturing method comprising a step of attaching at least a part of the surface on the fiber fabric side, and a step of peeling the release paper.

(3) Method for producing moisture-permeable waterproof fabric in which at least a part of both surfaces of a moisture-permeable waterproof layer made of polyurethane resin and a plurality of fiber fabrics are bonded to each other The permeability of the moisture-permeable waterproof fabric obtained in (1) above The manufacturing method including the process of apply | coating the adhesive agent of this invention on a moisture waterproof layer, and the process of sticking a fiber fabric on this adhesive layer.
In addition, as the polyurethane resin-forming composition for the moisture permeable and waterproof layer, known ones (for example, those described in JP-A No. 2007-211239) can be used.

Below, one manufacturing method of the dry-type laminating method applicable to said (1) is demonstrated in detail.
First, a coating liquid comprising the above-mentioned known polyurethane resin-forming composition for moisture permeable and waterproof layers is prepared, and this is coated on release paper using a knife coater, pipe coater, bar coater or the like. Then, it is dried with a dryer such as an air oven at about 100 to 160 ° C. for about 30 seconds to 5 minutes to form a moisture permeable waterproof layer made of polyurethane resin. The thickness of the moisture permeable waterproof layer can be adjusted by repeatedly adjusting the slit of the coater, applying, and drying when applying the coating liquid.

  Next, the adhesive of the present invention is applied on the obtained moisture permeable waterproof layer to form an adhesive layer. The adhesive is applied on the entire surface of the moisture-permeable waterproof layer using a gravure coater, knife coater, pipe coater, bar coater or the like, and is dried as necessary.

Next, a fiber fabric surface is affixed to the formed adhesive layer. The laminated body after pasting has a structure in which a fiber fabric, an adhesive layer, and a moisture permeable waterproof layer are sequentially stacked. The obtained laminate is subjected to thermocompression bonding at a temperature of 80 to 160 ° C. and aged at 30 to 110 ° C. for 20 to 100 hours as necessary.
Next, by separating the moisture permeable waterproof layer and the release paper, a moisture permeable waterproof fabric in which a moisture permeable waterproof layer made of polyurethane resin is formed in this order on one side of the fiber fabric via an adhesive layer is obtained.

  Further, if necessary, the obtained moisture-permeable waterproof fabric may be subjected to a water-repellent treatment using a fluorine-based or silicon-based water repellent. In addition, an adhesive is applied again on the moisture permeable waterproof layer after peeling the release paper (the surface on the opposite side of the previously bonded fiber fabric), and the other fabric fabric prepared in addition to that surface May be thermocompression-bonded in the same manner as described above, and a moisture permeable waterproof layer may be provided between the fiber fabric and the fiber fabric.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to this. In the following, “parts” represents parts by weight, and “%” represents% by weight.

The meanings of the abbreviations used in the production examples and examples are as follows.
OE group content: oxyethylene group content BD: 1,4-butanediol DADCHM: 4,4′-diaminodicyclohexylmethane DMF: dimethylformamide HDI: hexamethylene diisocyanate IPA: isopropyl alcohol IPDA: isophorone diamine IPDI: isophorone diisocyanate MEK: methyl ethyl ketone MPG: Propylene glycol monomethyl ether PBA: Polybutylene adipate diol PEA: Polyethylene adipate diol PEG: Polyoxyethylene glycol PEPG: Polyoxyethylene oxypropylene block copolymer diol PTMG: Polyoxytetramethylene glycol TDI: Tolylene diisocyanate TMDA: Trimethylhexa Methylenediamine TMDI: Tri Chill hexamethylene diisocyanate TMXDI: tetramethylxylylene diisocyanate

Production Example 1
In a reaction vessel equipped with a stirrer and a thermometer, 27 parts of PEPG of Mn (OH) 2,000 having an OE group content of 40% (calculated from the hydroxyl value, the same applies hereinafter), 130 parts of PEA of Mn (OH) 1,000 and IPDI39 .5 parts (NCO / OH reaction equivalent ratio = 1.24), reacted in a dry nitrogen atmosphere at 120 ° C. for 10 hours, cooled to 40 ° C., added with 283 parts of IPA, and uniformly dissolved. It was set as the prepolymer solution of terminal isocyanate. Separately, an amine solution in which 6.1 parts of DADCHM and 0.4 parts of diethanolamine (reaction terminator, hereinafter the same) are uniformly dissolved in 9.3 parts of IPA is added dropwise to the above prepolymer solution and reacted at 40 ° C. for 1 hour to make hydrophilic. An alcohol solution (solid content concentration 41%, viscosity 8,000 mPa · s / 20 ° C.) of polyurethane resin (A-1) (OE group content 5%) was obtained. The Mn of (A-1) was 38,000.

Production Example 2
In a reaction vessel similar to Production Example 1, 70 parts of PEG of Mn 1,500, 130 parts of PBA of Mn 1,000 and 67 parts of TMDI (NCO / OH reaction equivalent ratio = 1.81) were charged at 120 ° C. in a dry nitrogen atmosphere. After reacting for 7 hours, the mixture was cooled to 40 ° C., 268 parts of MPG was added and uniformly dissolved to obtain a prepolymer solution of both terminal isocyanates. Separately, an amine solution in which 22.5 parts of IPDA and 1 part of diethanolamine were uniformly dissolved in 23.6 parts of MPG was added dropwise to the prepolymer solution and reacted at 40 ° C. for 2 hours to obtain hydrophilic polyurethane resin (A-2) (OE group). An alcohol solution with a content of 24% (solid content concentration 50%, viscosity 30,000 mPa · s / 20 ° C.) was obtained. Mn of (A-2) was 27,000.

Production Example 3
A reaction vessel similar to Production Example 1 was charged with 162 parts of PEG of Mn 1,900, 107 parts of PBA of Mn 1,500 and 47 parts of IPDI (NCO / OH reaction equivalent ratio = 1.35) at 120 ° C. in a dry nitrogen atmosphere. After reacting for 9 hours, the mixture was cooled to 50 ° C., and 402 parts of IPA was added and dissolved uniformly to obtain a prepolymer solution of both terminal isocyanates. Separately, 8 parts of TMDA and an amine solution in which 0.3 part of diethanolamine is uniformly dissolved in 10.6 parts of IPA are dropped into the prepolymer solution and reacted at 40 ° C. for 2 hours to obtain hydrophilic polyurethane resin (A-3) (OE group content) 50%) of an alcohol solution (solid content concentration 44%, viscosity 20,000 mPa · s / 20 ° C.). Mn of (A-3) was 35,000.

Comparative production example 1
In a reaction vessel similar to Production Example 1, 100 parts of PEG of Mn 1,500, 100 parts of PEA of Mn 1,000, 8.7 parts of BD, 46 parts of TDI [NCO / OH (excluding BD) reaction equivalent ratio = 1.59] And 187 parts of DMF were charged and reacted at 70 ° C. for 11 hours in a dry nitrogen atmosphere to obtain a prepolymer solution of both terminal isocyanates. 124 parts of MEK was further added to the solution, and a DMF / MEK solution (solid content concentration 45%, viscosity 12,000 mPa · s / 20 ° C.) of hydrophilic polyurethane resin (ratio A-1) (OE group content 39%) was added. Obtained. The Mn of (Ratio A-1) was 35,000.

Comparative production example 2
A reaction vessel similar to Production Example 1 was charged with 11.0 parts of PEG of Mn 2,000, 200 parts of PEA of Mn 1,000 and 62 parts of TMXDI (NCO / OH reaction equivalent ratio = 1.24). After reacting at 10 ° C. for 10 hours, the mixture was cooled to 40 ° C., and 446 parts of MPG was added and uniformly dissolved to obtain a prepolymer solution of both terminal isocyanates. Separately, an amine solution in which 7 parts of TMDA and 0.5 part of diethanolamine were uniformly dissolved in 12.1 parts of MPG was added dropwise to the prepolymer solution and reacted at 40 ° C. for 2 hours to obtain a hydrophilic polyurethane resin (ratio A-2) (OE) An alcohol solution (solid content concentration 38%, viscosity 7,000 mPa · s / 20 ° C.) was obtained. Mn of (ratio A-2) was 43,000.

Comparative production example 3
A reaction vessel similar to Production Example 1 was charged with 150 parts of PEG of Mn 1,000, 30 parts of PEA of Mn 1,500 and 60.5 parts of IPDI (NCO / OH reaction equivalent ratio = 1.60). After reacting at 10 ° C. for 10 hours, the solution was cooled to 40 ° C., and 261 parts of IPA was added and uniformly dissolved to obtain a prepolymer solution of both terminal isocyanates. Separately, a mixed solution in which 8.8 parts of BD and 0.5 part of diethanolamine were uniformly dissolved in 10.1 parts of IPA was dropped into the prepolymer solution and reacted at 40 ° C. for 5 hours to obtain a hydrophilic polyurethane resin (ratio A-3). An alcohol solution (solid content concentration 48%, viscosity 22,000 mPa · s / 20 ° C.) with an OE group content of 60% was obtained. Mn of (Ratio A-3) was 32,000.

Production Example 4
Preparation of hydrophilic polyurethane resin for moisture permeable and waterproof layer: PEG 71 parts of Mn 1,000, PTMG 29 parts of Mn 1,000, and 62 parts of IPDI were charged (NCO / OH reaction equivalent ratio = 2.79), and 110 ° C. in a dry nitrogen atmosphere. Then, the mixture was cooled to 40 ° C. and 486 parts of IPA was added and uniformly dissolved to obtain a prepolymer solution. Separately, an amine solution in which 34.4 parts of DADCHM and 0.6 parts of diethanolamine were uniformly dissolved in 105 parts of IPA was added dropwise to the prepolymer solution and reacted at 40 ° C. for 1 hour to obtain hydrophilic polyurethane resin (Z) (OE group content 36 %) Alcohol solution (solid concentration 25%, viscosity 26,000 mPa · s / 20 ° C.). The Mn of (Z) was 37,000.

Example 1
Polyester taffeta (both warp and weft 83 decitex / 72 filaments, warp density 160 / 2.54 cm, weft density 70 / 2.54 cm, polyester taffeta thickness 0.1 mm) is scoured and dyed by conventional methods. Next, using a fluorine-based water repellent [a water repellent used before adhering the moisture permeable waterproof layer of fiber fabric and polyurethane resin, trade name “Asahi Guard AG710”, manufactured by Asahi Glass Co., Ltd., the same shall apply hereinafter] A water-processed product was used as a fiber fabric.
Next, the following coating liquid ZT was prepared, applied onto the entire surface of the release paper using a knife coater, and dried at 100 ° C. in an air oven to obtain a moisture-permeable waterproof layer having a thickness of 25 μm.
Coating liquid ZT
Alcohol solution of hydrophilic polyurethane resin (Z) 100 parts WB40-100 (urethane modified product of HDI) 4 parts IPA 40 parts

Next, the following coating liquid AT was prepared, applied onto the entire moisture permeable waterproof layer obtained above using a knife coater, and dried at 100 ° C. in an air oven to obtain a 25 μm thick adhesive layer.
Coating liquid AT
Alcohol solution of hydrophilic polyurethane resin (A-1) 100 parts WB40-100 7 parts IPA 30 parts

  Next, the fiber fabric and the adhesive layer on the moisture permeable waterproof layer were overlaid and bonded together using a nip roll heated to 100 ° C. Then, after aging at 70 ° C. for 72 hours, the release paper was peeled off. Further, the fiber fabric was subjected to water repellent treatment again using a fluorine-based water repellent to obtain a moisture permeable waterproof fabric (X-1).

Example 2
In the coating liquid AT of Example 1, a moisture-permeable waterproof fabric (X-2) was prepared in the same manner as in Example 1 except that the alcohol solution of (A-2) was used instead of the alcohol solution of (A-1). )

Example 3
In the coating liquid AT of Example 1, a moisture-permeable waterproof fabric (X-3) was obtained in the same manner as in Example 1 except that the alcohol solution of (A-3) was used instead of the alcohol solution of (A-1). )

Comparative Example 1
In the coating liquid AT of Example 1, 100 parts of the DMF / MEK solution (ratio A-1) was used instead of the alcohol solution (A-1), and DMF / MEK = 8/22 parts instead of 30 parts IPA. Except for using the mixed solvent, a moisture-permeable waterproof fabric (ratio X-1) was obtained in the same manner as in Example 1.

Comparative Example 2
In the coating liquid AT of Example 1, a moisture-permeable waterproof fabric (ratio X) was used in the same manner as in Example 1 except that the alcohol solution of (A-2) was used instead of the alcohol solution of (A-1). -2) was obtained.

Comparative Example 3
In the coating liquid AT of Example 1, in the same manner as in Example 1 except that the alcohol solution of (A-3) was used instead of the alcohol solution of (A-1), a moisture-permeable waterproof fabric (ratio) X-3) was obtained.

The following performance evaluation was performed about the moisture-permeable waterproof fabric obtained above. The results are shown in Table 1.
Performance evaluation (1) Moisture permeability It evaluated by measuring moisture permeability according to the potassium acetate method (B-1 method) in JISL1099 (moisture permeability test method of textiles).

(2) Waterproofness It evaluated by measuring a water resistance according to JIS L 1092 (the high water pressure method of the hydrostatic pressure method of the waterproof test method of a textile product). In addition, when the test piece is stretched by applying water pressure, a nylon taffeta (density: vertical + horizontal = about 210 pieces / 2.54 cm) is stacked on the test piece and then attached to the tester for measurement. It was.
Further, the unit of waterproofness in the high water pressure method of JIS L 1092 is kPa, but here it is expressed in mmH ₂ O converted to the water column used in the low water pressure method.
(3) Peel strength The peel strength in the longitudinal direction was measured according to JIS L 1089 method.
(4) Flexibility Evaluation was made based on the following criteria based on hand touch.
Evaluation Criteria 1 Very soft 2 Soft 3 Slightly hard 4 Hard (5) Washing resistance In order to check the moisture permeability, waterproofness, peel strength, flexibility change and appearance change for washing, The items (1) to (4) and the appearance were evaluated. Washing was carried out 10 times according to JIS L 0217 103 method as washing conditions, and the appearance was evaluated according to the following criteria.
Evaluation criteria ○ No change in appearance × Peeling or floating

  From the results in Table 1, the adhesive of the present invention has a smaller environmental load than the comparative one, is excellent in adhesion between the moisture permeable waterproof layer and the fiber fabric, and is moisture permeable obtained by using the adhesive. It can be seen that the waterproof fabric is excellent in moisture permeability, waterproofness and washing resistance and has a soft texture.

  The moisture-permeable waterproof fabric using the adhesive for moisture-permeable waterproof fabric of the present invention is suitable for a wide range of uses such as clothing [sportswear (ski wear, golf wear, etc.), fishing / hunting wear, etc.], and tents. Therefore, the adhesive for moisture-permeable waterproof fabric of the present invention and the moisture-permeable waterproof fabric using the adhesive are extremely useful.

Claims (4)

  A chain extender comprising a polymer diol (a) containing a polymer diol (a1) having an oxyethylene group, an aliphatic and / or alicyclic diisocyanate (b), and an aliphatic and / or alicyclic diamine ( A moisture-permeable waterproof fabric adhesive comprising a hydrophilic polyurethane resin (A) formed from c) and an alcohol solution consisting of an alcohol solvent (B) and a polyisocyanate (C).   The adhesive according to claim 1, wherein the oxyethylene group content of (A) is 5 to 50% by weight.   At least a part of at least one side of the fiber fabric and a moisture permeable waterproof layer made of polyurethane resin are bonded via an adhesive layer formed from the adhesive according to claim 1 or 2, or made of polyurethane resin. A moisture permeable waterproof fabric in which at least a part of both surfaces of a moisture permeable waterproof layer is bonded to a plurality of fiber fabrics.   One side of the fiber fabric is provided on the side of the laminated layer obtained by laminating the release paper, the moisture-permeable waterproof layer made of polyurethane resin, and the adhesive layer formed of the adhesive according to claim 1 in this order. A method for producing a moisture-permeable waterproof fabric, wherein the release paper is peeled off after at least a part of each is bonded.